JP7405110B2 - Active energy ray-curable adhesive composition, adhesive layer, laminate - Google Patents

Description

The present invention relates to an active energy ray-curable adhesive composition, an adhesive layer, and a laminate.

Adhesives are used to bond various parts together in the manufacturing process of mobile devices such as smartphones and tablets, digital home appliances such as digital cameras and audio devices, and communication devices such as radios and modems. Among them, highly transparent adhesives are used for bonding optical components together, such as bonding touch sensors and front panels when manufacturing touch panels, and bonding touch sensors and image display devices. .

In general, such adhesives have flexibility, so when applied to a component, they make it easier to process the component, but the laminate itself becomes soft, so for example, in a laminate with a hard coat layer, it is difficult to process the component. When the surface hardness of the coat layer is measured, scratches and dents are likely to occur on the surface, and the hard coat layer's original function of preventing scratches is lost. In order to maintain this function, it is effective to increase the elastic modulus of the adhesive layer, but increasing the elastic modulus of the adhesive layer tends to reduce the adhesive force, and it is a challenge to achieve both of these.

As a technique for solving these problems, for example, in an active energy ray-curable adhesive composition (Patent Document 1) containing polyurethane (meth)acrylate, a hydroxyl group-containing polymerizable monomer, and a heterocycle-containing polymerizable monomer, the adhesive Although high hardness of the layer was achieved, the adhesive layer itself was hard, resulting in insufficient adhesive strength. In addition, in a thermosetting adhesive composition containing an ultraviolet (meth)acrylic copolymer, a polyisocyanate crosslinking agent, and an organic solvent (Patent Document 2), although the adhesive layer has excellent flexibility and adhesive strength, The rate was likely to decrease.

Patent No. 6610256 Japanese Patent Application Publication No. 2015-174907

An object of the present invention is to increase the elastic modulus of the adhesive layer so that the hard coat layer is hard enough to prevent damage, and the adhesive layer exhibits excellent adhesive strength. An object of the present invention is to provide a drug composition.

After intensive study, the present inventors found that the above problem can be solved by incorporating a large amount of a monofunctional monomer having a glass transition temperature above a certain level. That is, the present invention relates to the following active energy ray-curable adhesive composition, adhesive layer, and laminate.

1. It is a reaction product of polyol (a1), polyisocyanate (a2), and mono(meth)acrylate (a3-1) having a hydroxy group or mono(meth)acrylate (a3-2) having an isocyanate group, and has one molecule. A polyurethane (meth)acrylate (A) having an average number of (meth)acryloyl groups of 1 to 4 and a weight average molecular weight of 10,000 to 90,000;
A monomer (B) having one ethylenically unsaturated double bond in the molecule and having no hydroxyl group and having a glass transition temperature of 40° C. or higher when made into a homopolymer;
Monomer (C) having one ethylenically unsaturated double bond and a hydroxy group in the molecule
An active energy ray-curable adhesive composition containing 35 to 75% by mass of component (B) in a total of 100% by mass of components (A), (B), and (C). .

2. The active energy ray-curable adhesive composition according to item 1 above, wherein component (a1) contains a polyether polyol.

3. 3. The active energy ray-curable adhesive composition according to item 1 or 2 above, wherein component (B) contains an alicyclic mono(meth)acrylate.

4. 4. The active energy ray-curable adhesive composition according to any one of items 1 to 3 above, wherein component (C) contains a monohydroxyalkyl mono(meth)acrylate.

5. The active energy ray-curable adhesive composition according to any one of items 1 to 4 above, further comprising (D) a tackifying resin.

6. An adhesive layer of the active energy ray-curable adhesive composition according to any one of items 1 to 5 above.

7. 7. The adhesive layer according to item 6, wherein the storage elastic modulus G' at a temperature of 25° C. and a frequency of 1 Hz is 0.5 MPa or more.

8. A laminate having an adhesive layer according to item 6 or 7 above on at least one side of a base material.

9. A laminate having a pressure-sensitive adhesive layer according to item 6 or 7 above on one side of a base material and a hard coat layer on the other side.

The active energy ray-curable adhesive composition (hereinafter simply referred to as "adhesive composition") according to the present invention has a high elastic modulus of the adhesive layer, so it has a hardness that does not damage the hard coat layer. . Furthermore, the adhesive layer has excellent adhesive strength and durability.

Diagram of the method for manufacturing the laminate (1) in Example Diagram of the method for manufacturing the laminate (2) in Example Diagram of the layer structure of the laminate (1) obtained in Figure 1 Diagram of the layer structure of the laminate (2) obtained in Figure 2

The adhesive composition of the present invention has a specific polyurethane (meth)acrylate (A) (hereinafter referred to as component (A)) in its molecule, which has a glass transition temperature of 40°C or higher when made into a homopolymer. A monomer (B) that has one ethylenically unsaturated double bond and does not have a hydroxyl group (hereinafter referred to as component (B)), and a monomer that has one ethylenically unsaturated double bond in the molecule. and a monomer (C) having a hydroxy group (hereinafter referred to as component (C)).

Component (A) of the present invention includes polyol (a1) (hereinafter referred to as component (a1)), polyisocyanate (a2) (hereinafter referred to as component (a2)), and a mono(meth) having a hydroxy group. It is a reaction product of acrylate (a3-1) (hereinafter referred to as component (a3-1)) or mono(meth)acrylate (a3-2) having an isocyanate group (hereinafter referred to as component (a3-2)). .

Component (a1) refers to an alcohol having two or more hydroxy groups, and is a component used in order for the adhesive layer to exhibit excellent adhesive strength. As component (a1), single compound polyols and polymer polyols can be used, and crystalline polyols and amorphous polyols can also be used. Here, the crystalline polyol refers to a polyol having a crystal structure preferably at 20 to 60°C, more preferably at 20 to 40°C.

The polyol as a single compound is not particularly limited, and includes, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1 , 5-pentanediol, 2,2-diethyl-1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, butylethylpropanediol, butylethylpentanediol and other aliphatic diols; 1, Alicyclic diols such as 4-cyclohexanedimethanol; trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, dimer diol, hydrogenated dimer diol, trimer triol, hydrogenated trimer triol, castor oil, castor oil-based modification Examples include alkylene oxide adducts of polyols, bisphenol compounds, or derivatives thereof. These may be used alone or in combination of two or more.

The polymer polyol is not particularly limited, and examples thereof include polyether polyol, polyester polyol, poly(meth)acrylic polyol, polyolefin polyol, polycaprolactone polyol, polycarbonate polyol, and the like. These may be used alone or in combination of two or more. Note that (meth)acrylic means acrylic or methacryl.

Among these, polymer polyols are preferred from the viewpoint of high adhesive strength of the adhesive layer. Specific polymer polyols are listed below.

The polyether polyol is not particularly limited, and includes, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, as well as a plurality of alkylene oxides as monomer components such as ethylene oxide-propylene oxide copolymer. Examples include copolymers containing (alkylene oxide-other alkylene oxide). These may be used alone or in combination of two or more.

Commercially available polyether polyols include ``ADEKA Polyether P-400'', ``ADEKA Polyether G-400'', ``ADEKA Polyether T-400'', ``ADEKA Polyether AM-302'', and ``ADEKA Polyether P1000''. ”, “ADEKA Polyether P2000” (manufactured by ADEKA Co., Ltd.); “Polyethylene Glycol #1,540” (manufactured by Nacalai Tesque Co., Ltd.); “Dipropylene Glycol”, “Polypropylene Glycol 400” (all genuine products) (manufactured by Kagaku Corporation); "PTMG650", "PTMG1000", "PTMG2000", "PTMG3000" (manufactured by Mitsubishi Chemical Corporation), and the like.

Polyester polyols are not particularly limited, and include, for example, condensation polymers of polyols and polycarboxylic acids; ring-opening polymers of cyclic esters (lactones); three-way reaction products of polyols, polycarboxylic acids, and cyclic esters. It will be done.

The polyol is not particularly limited, and includes, for example, those listed above as polyols as a single compound; triols such as glycerin, trimethylolpropane, and trimethylolethane; 1,2-cyclohexanediol, 1,3-cyclohexane Diol, cyclohexanediols such as 1,4-cyclohexanediol; cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; bisphenol A, bisphenol F, etc. bisphenols; sugar alcohols such as xylitol and sorbitol; these may be used alone or in combination of two or more.

Polycarboxylic acids are not particularly limited, and include, for example, aliphatic dicarboxylic acids such as malonic acid, maleic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; 1,4-cyclohexanedicarboxylic acid; Alicyclic dicarboxylic acids such as acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, etc., and these can be used alone or in combination of two or more. Also good.

The cyclic ester is not particularly limited and includes, for example, propiolactone, β-methyl-δ-valerolactone, ε-caprolactone, etc., and these may be used alone or in combination of two or more.

Commercially available polyester polyols include "Polylite RX-4800," "Polylite OD-X-2523," "Polylite OD-X-2547," "Polylite OD-X-2420," and "Polylite OD-X-2692." , "Polylite OD-X-2108" (manufactured by DIC Corporation); "Kuraray Polyol P-510", "Kuraray Polyol P-1010", "Kuraray Polyol P-2010", "Kuraray Polyol F-510" (all manufactured by Kuraray Co., Ltd.), etc.

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene; a ring-opening polymer of a cyclic carbonate (alkylene carbonate, etc.), and the like. Examples of the polyol include those mentioned above. The alkylene carbonate is not particularly limited, and examples thereof include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, hexamethylene carbonate, and the like. Commercially available polycarbonate polyols include "Kuraray Polyol C-590" (manufactured by Kuraray Co., Ltd.); "Nipporan 4002", "Nipporan 4009", "Nipporan 981" (all manufactured by Tosoh Corporation); and "Duranol T6002". ”, “Duranol T5652” (manufactured by Asahi Kasei Corporation), and the like.

Examples of poly(meth)acrylic polyols include homopolymers or copolymers of acrylic monomers having one or more hydroxyl groups, or copolymers of these copolymers with other monomers. These may be used alone or in combination of two or more.

Commercially available poly(meth)acrylic polyols include "ARUFON UH-2041" (manufactured by Toagosei Co., Ltd.); "acrylic polyol #6000" (manufactured by Taisei Fine Chemical Co., Ltd.); "acrylic polyol PC #5984" (manufactured by Taisei Fine Chemical Co., Ltd.); (manufactured by Toei Kasei Co., Ltd.), etc.

The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxy groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, and chlorinated products thereof. These may be used alone or in combination of two or more. Commercially available products include "NISSO-PB GI-1000," "NISSO-PB GI-2000," and "NISSO-PB GI-3000" (all manufactured by Nippon Soda Co., Ltd.).

The polycaprolactone polyol is not particularly limited, and examples thereof include polycaprolactone diol, polycaprolactone triol, polycaprolactone tetraol, and the like, and these may be used alone or in combination of two or more types. Commercially available products include "Polylite OD-X-2155" (manufactured by DIC Corporation); "Plaxel 200", "Plaxel 205", "Plaxel 300", "Plaxel 400" (all manufactured by Daicel Corporation), etc. can be mentioned.

Among these polymer polyols, polyether polyols, polyester polyols, and polycaprolactone polyols are preferred, and polyether polyols are more preferred, from the viewpoint of high adhesive strength and excellent durability of the adhesive layer.

The physical properties of component (a1) are not particularly limited, and for example, the number average molecular weight (polystyrene equivalent value determined by gel permeation chromatography (GPC method)) is such that the adhesive layer has both high adhesive strength and elastic modulus. Therefore, it is usually about 700 to 10,000, preferably about 1,000 to 4,000.

In addition, the average number of hydroxy groups per molecule of component (a1) (hereinafter also simply referred to as "average hydroxy group number") is usually about 1.5 to 3, preferably 2, from the viewpoint of high adhesive strength of the adhesive layer. It is about ~3.

The average number of hydroxy groups per molecule of component (a1) is the average number of hydroxy groups present in one molecule of component (a1). For example, since ethylene glycol has two hydroxy groups in one molecule, the average number of hydroxy groups is "2". Furthermore, when a plurality of components (a1) having different numbers of hydroxy groups are used, for example, when 0.4 mol of ethylene glycol (number of hydroxy groups: 2) and 0.6 mol of trimethylolpropane (number of hydroxy groups: 3) are used, The average number of hydroxy groups can be determined by weighted average.
(Formula 1) [Average number of hydroxy groups per molecule of component (a1)]
=(2×0.4+3×0.6)/(0.4+0.6)=2.6

Component (a2) is not particularly limited, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1 , 4-cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and other aliphatic diisocyanates. These may be used alone or in combination of two or more. Further, as the component (a2), a nurate, adduct or biuret of these may be used. Among these, aliphatic diisocyanates are preferred since the adhesive layer has excellent durability.

The usage ratio of component (a1) and component (a2) is not particularly limited, and usually the number of moles of isocyanate groups (NCO _(a2) ) of component (a2) and the number of moles of hydroxyl groups (OH The ratio (NCO ( _{a2 )} /OH _(a1) ) to (a1) ) is preferably about 1.01 to 2.

Component (a3-1) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate. Examples include acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate. These may be used alone or in combination of two or more. Among these, hydroxy group-containing mono(meth)acrylate and/or hydroxy group-containing di(meth)acrylate are preferred from the viewpoint that the adhesive layer has a high elastic modulus, and 2-hydroxyethyl (meth)acrylate, 4- Hydroxybutyl (meth)acrylate is more preferred. Note that (meth)acrylate means acrylate or methacrylate.

Furthermore, in the present invention, poly(meth)acrylate having a hydroxy group may be used in combination with component (a3-1). Examples of the poly(meth)acrylate include hydroxy groups such as 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, pentaerythritol di(meth)acrylate, and 2-hydroxy-1,3-di(meth)acrylate. Di(meth)acrylate having a hydroxy group; tri(meth)acrylate having a hydroxy group such as pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate; having a hydroxy group such as dipentaerythritol tetra(meth)acrylate Examples include penta(meth)acrylates having a hydroxy group such as tetra(meth)acrylate; dipentaerythritol penta(meth)acrylate, and these may be used alone or in combination of two or more.

The component (a3-2) is not particularly limited, and various known components can be used. Examples include 2-isocyanatoethyl (meth)acrylate, 2-(o-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, and these may be used alone or in combination of two or more.

Component (A) is not particularly limited, and can be produced by various known methods. Hereinafter, as the (a3) component, the (A1) component obtained using the (a3-1) component (hereinafter referred to as the (A1) component), and as the (a3) component, the (A1) component obtained using the (a3-2) component. (A2) component (hereinafter referred to as (A2) component) will be explained separately.

Component (A1) is not particularly limited. For example, component (a1) and component (a2) are reacted to produce an isocyanate group-terminated urethane prepolymer (hereinafter referred to as component (A1')), and then (A1' ) and (a3-1) are reacted. The reaction conditions are not particularly limited, but usually the temperature is about 70 to 85°C and the time is about 1 to 5 hours. In addition, the usage ratio of component (a1) and component (a2) is not particularly limited, but the number of moles of isocyanate groups in component (a2) (NCO _(a2) ) and the number of moles of hydroxyl groups in component (a1) (OH _(a1) ) (NCO _(a2) /OH _(a1) ) is usually within a range of about 1.01 to 2. Furthermore, the usage ratio of component (A1') and component (a3-1) is not particularly limited, but the number of moles of isocyanate groups in the former (NCO _(A1') ) and the number of moles of hydroxyl groups in the latter (OH _{(a3- 1)} ) (NCO _(A1') /OH _(a3-1) ) is usually within a range of about 0.25 to 1.

Component (A2) is prepared by reacting component (a1) with component (a2) to obtain a hydroxy group-terminated urethane prepolymer (hereinafter referred to as component (A2')), and then combining component (A2') with component (a3-2). ) components may be reacted. The reaction temperature and reaction time are the same as for component (A1). Further, the usage ratio of component (a1) and component (a2) is not particularly limited, but may be within a range where (NCO _(a2) /OH _(a1) ) is usually about 0.50 to 0.99. Furthermore, the usage ratio of component (A2') and component (a3-2) is not particularly limited, but the number of moles of isocyanate groups in the latter (NCO _(a3-2) ) and the number of moles of hydroxyl groups in the former (OH _{(A2 ')} ) (NCO _(a3-2) /OH _(A2') ) is usually within a range of about 0.5 to 1.

Although the production of these components (A1) and (A2) may be carried out in the presence of an organic solvent, which will be described later, it is preferable to carry out the production without a solvent in order to reduce the environmental burden. Moreover, in these productions, it can also be carried out in the presence of component (B), which will be described later.

The weight average molecular weight of the obtained component (A) is 10,000 to 90,000. If the weight average molecular weight is less than 10,000, the adhesive force of the adhesive layer will not be sufficiently exerted due to the low molecular weight, and if it exceeds 90,000, the elastic modulus of the adhesive layer will decrease and the hard coat The layer's ability to prevent scratches becomes insufficient. Also, from the same tendency, the weight average molecular weight of component (A) is preferably 20,000 to 80,000, more preferably 20,000 to 70,000. The weight average molecular weight is a value measured by gel permeation chromatography (GPC method) using polystyrene as a standard substance.

Further, the average number of (meth)acryloyl groups per molecule of component (A) (hereinafter also simply referred to as "average (meth)acryloyl group number") is 1 to 4. When the average (meth)acryloyl group number is within this range, the adhesive layer has high adhesive strength. Also, from the same tendency, the average number of (meth)acryloyl groups is preferably 1 to 3, more preferably 1 to 2. Note that the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

The average number of (meth)acryloyl groups per molecule of component (A) refers to the average number of (meth)acryloyl groups present per molecule of component (A). For example, when 1 mole of ethylene glycol, 2 moles of diisocyanate as component (a2), and 2 moles of component (a3-1) are reacted, the average number of (meth)acryloyl groups is "2".

In addition, component (A) may contain two or more substances having the same or different average (meth)acryloyl groups, or may be mixed, and the average (meth)acryloyl groups in this case can be determined by a weighted average. can. For example, if it contains 0.2 moles of component (A) with an average number of (meth)acryloyl groups of 1 and 0.8 moles of component (A) with an average number of (meth)acryloyl groups of 2, the following will be obtained. .
(Formula 2) [Average number of (meth)acryloyl groups per molecule of component (A)]
=(1×0.2+2×0.8)/(0.2+0.8)=1.8

Since the adhesive layer has a high elastic modulus, the content of component (A) is usually determined by the solid mass (the same applies hereinafter), and the total of component (A), component (B), and component (C). As 100% by mass, it is 20 to 60% by mass, preferably 30 to 60% by mass, and more preferably 30 to 55% by mass.

Component (B) is a monomer that has one ethylenically unsaturated double bond in the molecule and has no hydroxyl group, and has a glass transition temperature of 40°C or higher when made into a homopolymer. This is a component that allows the adhesive layer cured with the adhesive composition of the invention to exhibit a high elastic modulus.

"Glass transition temperature when made into a homopolymer" refers to the glass transition temperature (Tg) of a polymer produced by polymerizing only the monomer alone. For example, "POLYMER HANDBOOK FOURTH EDITION" by Wiley-Interscience. (2003) describes specific numerical values. In the present invention, the values described in the product information on the homepages and catalogs of chemical manufacturers were adopted. When the glass transition temperature is 40° C. or higher, the elastic modulus of the adhesive layer becomes high, and when a laminate having a hard coat layer is formed, the hard coat layer is less likely to be damaged. From the same point of view, the glass transition temperature is preferably 50 to 250°C, more preferably 60 to 200°C.

Component (B) includes, for example, aliphatic mono(meth)acrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, and t-butyl methacrylate; isobornyl acrylate; Isobornyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, 3,3,5-trimethylcyclohexyl methacrylate, 4-t-butylcyclohexyl methacrylate, cyclooctyl methacrylate, dicyclopentanyl acrylate, di Alicyclic mono(meth)acrylates such as cyclopentenyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, 1-adamantyl acrylate, 3,5-dimethyladamantyl acrylate, 1-adamantyl methacrylate; Examples include aromatic mono(meth)acrylates such as phenyl acrylate, phenyl methacrylate, benzyl methacrylate, 2-phenoxyethyl methacrylate, and 2-naphthyl acrylate, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used alone or in combination of two or more. Among these, alicyclic (meth)acrylates are preferred, and isobornyl acrylates are preferable because the adhesive layer has excellent durability and has a high elastic modulus, making the hard coat layer less likely to be scratched. , 3,3,5-trimethylcyclohexyl acrylate is more preferred.

The content of component (B) is 35 to 75% by mass in 100% by mass of the total of components (A), (B) and (C). If the content of component (B) is less than 35% by mass, the elastic modulus of the adhesive layer will be low, and the hard coat layer will be easily damaged or deformed. Moreover, if the content exceeds 75% by mass, the adhesive force of the adhesive layer will be difficult to exhibit. It is preferably 35 to 70% by weight, more preferably 40 to 65% by weight.

Component (C) is a monomer having one ethylenically unsaturated double bond and a hydroxy group in the molecule, and in the adhesive composition of the present invention, the adhesive layer has a high elastic modulus and an excellent It is a component that provides both adhesive strength.

Component (C) is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, Monohydroxyalkyl mono(meth)acrylates such as 4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate, 8-hydroxyoctyl(meth)acrylate; 2,3-dihydroxypropyl(meth)acrylate, 3, Dihydroxyalkyl mono(meth)acrylates such as 4-dihydroxybutyl(meth)acrylate, glycerin mono(meth)acrylate, 1,4-dihydroxyheptyl(meth)acrylate; 4-hydroxycyclohexyl(meth)acrylate, 3-hydroxy-1 -Alicyclic mono(meth)acrylates with monohydroxy groups such as adamantyl (meth)acrylate; dihydroxy groups such as 1,4-cyclohexanedimethanol mono(meth)acrylate and 3,5-dihydroxyadamantyl(meth)acrylate Monohydroxy aromatic (meth)acrylates such as alicyclic mono(meth)acrylates and 2-hydroxy-3-phenoxypropyl (meth)acrylates; hydroxyvinyl acetate, hydroxypropanoic acid vinyl, hydroxybutanoic acid vinyl, hydroxyhexanoic acid Monohydroxy aliphatic carboxylic acid vinyl esters such as vinyl; monohydroxy alicyclic carboxylic acid vinyl esters such as 4-hydroxycyclohexyl vinyl acetate; allyl hydroxyacetate, allyl hydroxypropanoate, allyl hydroxybutanoate, allyl hydroxyhexanoate, etc. Monohydroxycarboxylic acid aliphatic allyl ester; monohydroxycarboxylic acid alicyclic allyl ester such as 4-hydroxycyclohexyl allyl acetate, and the like. These may be used alone or in combination of two or more. Among them, from the viewpoint of excellent durability of the adhesive layer, monohydroxyalkyl mono(meth)acrylate is preferred, and 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are more preferred.

From the viewpoint of excellent durability and high adhesive strength of the adhesive layer, the content of component (C) is usually determined in 100% by mass of the total of components (A), (B), and (C). , 3 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 15% by weight.

The adhesive composition of the present invention may further contain a tackifier resin (D) (hereinafter referred to as component (D)). Examples of the component (D) include rosin resins, aliphatic petroleum resins, aromatic petroleum resins, phenol resins , xylene resins, coumaron-indene resins, terpene resins, and hydrides of these resins. . These may be used alone or in combination of two or more.

Rosin-based resins include, for example, unmodified rosins such as gum rosin, tall oil rosin, wood rosin, Mercushi pine rosin, and marsh pine rosin; disproportionated rosin, polymerized rosin, acrylated rosin, maleated rosin, fumarated rosin, and rosin. Examples include modified rosins such as esters and polymerized rosin esters (eg, esters include methyl esters, glycerin esters, diglycerin esters, pentaerythritol esters, etc.). Note that modified rosin (excluding disproportionated rosin) can also be used in the form of a hydride.

Commercially available products of component (D) include, for example, "Pencel D-135," "Super Ester A-125," "Pine Crystal KE-100," "Pine Crystal KE-311," and "Pine Crystal KE-604." , “Alcon P-100”, “Alcon M-100”, “Alcon M-135”, “Alcon P-140” (manufactured by Arakawa Chemical Industry Co., Ltd.), “YS Polyster TH130”, “YS Polyster G150”, Examples include "YS Polyster T-160" (manufactured by Yasuhara Chemical Co., Ltd.).

The content of component (D) is not particularly limited, but from the viewpoint of increasing the adhesive force and elastic modulus of the adhesive layer, the content of component (D) is based on a total of 100 parts by mass of components (A), (B), and (C). The amount is preferably 1 to 20 parts by weight, more preferably 5 to 10 parts by weight.

The adhesive composition of the present invention may further contain a polyfunctional monomer since the adhesive layer has a high elastic modulus. For example, hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta( Examples include (meth)acrylates such as meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy(meth)acrylate, polyester(meth)acrylate, and urethane(meth)acrylate. These may be used alone or in combination of two or more. Further, the amount of the polyfunctional monomer used is not particularly limited, and is usually 10% by mass or less, preferably 5% by mass or less, based on 100 parts by mass of the adhesive composition according to the present invention.

The adhesive composition of the present invention may contain various known additives, if necessary. Additives are not particularly limited, and include, for example, surface conditioners, surfactants, ultraviolet absorbers, antioxidants, light stabilizers, inorganic fillers, silane coupling agents, colloidal silica, antifoaming agents, wetting agents, Examples include rust preventives. These may be used alone or in combination of two or more.

The adhesive composition of the present invention is obtained by mixing component (A), component (B), component (C), and, if necessary, component (D), the polyfunctional monomer, and additives. The mixing means and mixing order are not particularly limited. In addition, when the (A) component is diluted with the (B) component, the (C) component, if necessary, the (D) component, the monomers and additives mentioned above, are added to the solution of the (B) component of the (A) component. All you have to do is mix them.

The adhesive composition of the present invention is substantially solvent-free, but may contain an organic solvent as long as the content is less than 1% by mass, preferably less than 0.1% by mass. Note that the organic solvents used here include aromatic solvents such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, and aromatic naphtha. Group hydrocarbons; aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane; alicyclic hydrocarbons such as cyclohexane; ethyl acetate, n-butyl acetate, n-amyl acetate, Esters such as 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, methyl benzoate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol Glycol ethers such as monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t -Alcohols such as butanol can be mentioned.

The adhesive composition of the present invention contains a photopolymerization initiator upon irradiation with active energy rays. The photopolymerization initiator is not particularly limited, and includes, for example, photopolymerization initiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and oxime ester compounds, and photosensitizers such as amines and quinones. More specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy- 2-Methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-(dimethylamino )-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-phenylphosphine oxide, bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl) Titanium, 1,2-octanedione 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-1-(o-acetyloxime) and the like. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator is not particularly limited, but from the viewpoint of curability of the adhesive composition and high elastic modulus of the adhesive layer, the content of the photopolymerization initiator is based on a total of 100 parts by weight of components (A) to (D). , usually about 0.1 to 10 parts by weight, preferably about 0.2 to 7 parts by weight, more preferably about 0.2 to 2 parts by weight.

The cured product of the present invention is obtained by curing the pressure-sensitive adhesive composition.

The laminate of the present invention has the cured product on at least one side of the base material.

The laminate of the present invention can be obtained by applying the pressure-sensitive adhesive composition to a base material and then irradiating the base material with active energy rays.

The base material is not particularly limited, but includes, for example, polyethylene terephthalate (PET), cycloolefin polymer (COP), polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyethylene naphthalate, and Examples include butylene terephthalate, polyurethane, ethylene vinyl acetate, ionomer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, polystyrene, polycarbonate, polyimide, fluororesin, and the like. Moreover, you may use these crosslinked films or laminated films. These films may be untreated, lightly or heavily peeled, or provided with an easily adhesive layer.

Further, the coating method is not particularly limited, and examples thereof include an applicator, a bar coater, a roll coater, a die coater, a comma coater, a knife coater, a gravure coater, and the like. The amount of active energy ray-curable pressure-sensitive adhesive composition to be applied is not particularly limited, and it is usually applied so that the thickness of the cured product is 10 to 500 μm, preferably 25 to 250 μm.

The active energy rays are not particularly limited, and examples include light rays such as ultraviolet rays, infrared rays, and visible rays, electron beams, X-rays, α-rays, β-rays, γ-rays, and neutron beams. In the present invention, light is preferred, and ultraviolet light is more preferred.

The ultraviolet light source is not particularly limited, and examples thereof include a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and the like. Further, the cumulative amount of ultraviolet light and the conveying speed are not particularly limited, and the cumulative amount of ultraviolet light is usually about 100 to 3000 mJ/cm ² and the conveying speed is usually about 5 to 50 m/min.

Further, one embodiment of the present invention is a laminate having a cured product of the pressure-sensitive adhesive composition on one side of the base material and a hard coat layer on the other side.

As the hard coat agent used in the hard coat layer, various known hard coat agents such as acrylic resin, urethane resin, silicone resin, and epoxy resin can be used. Further, the method for forming the hard coat layer includes the same method as the method for forming the cured product described above. In addition, the order of forming the hard coat layer is such that the hard coat agent is first applied to the base material and cured, and then the cured product of the adhesive composition is provided on the surface not coated with the hard coat agent. Alternatively, after providing a cured product of the pressure-sensitive adhesive composition on the base material, a hard coat agent may be applied to the surface not coated with the pressure-sensitive adhesive and cured. The structure of the laminated film with a hard coat layer is hard coat layer/base film/adhesive layer/release PET film. The thickness of the hard coat layer is also not particularly limited, and is usually 1 to 20 μm, preferably 1 to 10 μm. Examples of the structure of the laminate include a structure of hard coat layer/base film/adhesive layer/glass.

Hereinafter, the present invention will be specifically explained through Examples and Comparative Examples. It goes without saying that the technical scope of the present invention is not limited thereby. "Parts" and "%" in the examples are based on mass unless otherwise specified.

Manufacturing example 1
In a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 856 parts of polypropylene glycol (trade name: "ADEKA Polyether P-2000", manufactured by ADEKA Corporation) (hereinafter referred to as PPG2000) having a number average molecular weight of 2000, and isophorone were added. 119 parts of diisocyanate (hereinafter referred to as IPDI), 0.4 parts of methoquinone (hereinafter referred to as MQ), and 0.1 part of stannous octylate were added, and the temperature was raised to 70°C and kept for 3 hours. An isocyanate group-terminated urethane prepolymer was obtained. Subsequently, 25 parts of 2-hydroxyethyl acrylate (hereinafter referred to as HEA) was added, kept at 70°C for 2 hours, and the isocyanate value (hereinafter referred to as NCO value) was measured to confirm the completion of the reaction, and the weight average molecular weight was determined. 26,000 and an average number of acryloyl groups of 2 was obtained. Note that the NCO value was measured in accordance with JIS K 1603-1 (the same applies hereinafter).

Manufacturing example 2
870 parts of PPG2000, 113 parts of IPDI, 0.4 parts of MQ, and 0.1 part of stannous octylate were added to a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, and the temperature was raised to 70°C and kept for 3 hours. After that, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 17 parts of HEA was added, kept at 70°C for 2 hours, and the completion of the reaction was confirmed by measuring the NCO value. (A-2) with a weight average molecular weight of 39,000 and an average number of acryloyl groups of 2 was obtained. Got the ingredients.

Manufacturing example 3
860 parts of PPG2000, 119 parts of IPDI, 0.4 parts of MQ, and 0.1 part of stannous octylate were added to a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and the temperature was raised to 70°C and kept at the temperature for 3 hours. After that, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 13 parts of HEA and 8 parts of n-butanol were added, kept at 70°C for 2 hours, and the completion of the reaction was confirmed by measuring the NCO value. As a result, the weight average molecular weight was 28,000 and the average number of acryloyl groups was 1. Component (A-3) was obtained.

Production example 4
Poly(3-methyl-1,5-pentylene adipate) glycol (trade name: "Kuraray Polyol P2010", manufactured by Co., Ltd.) with a number average molecular weight of 2,000 was added to a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. (manufactured by Kuraray) (hereinafter referred to as P2010), 856 parts of IPDI, 119 parts of MQ, and 0.1 part of stannous octylate were added, and the temperature was raised to 70°C and kept for 3 hours, and then the isocyanate intermediate was added. A group-terminated urethane prepolymer was obtained. Subsequently, 25 parts of HEA was added, kept at 70°C for 2 hours, and the completion of the reaction was confirmed by measuring the NCO value. Got the ingredients.

Manufacturing example 5
870 parts of PPG2000, 113 parts of IPDI, 0.4 parts of MQ, and 0.1 part of stannous octylate were added to a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, and the temperature was raised to 70°C and kept for 3 hours. After that, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 8 parts of HEA and a mixture of pentaerythritol triacrylate/pentaerythritol tetraacrylate (trade name: "Aronix M-306", manufactured by Toagosei Co., Ltd., weight ratio of pentaerythritol triacrylate 65 to 70%) 9 By adding 50% of the mixture, keeping it warm at 70°C for 2 hours, and confirming the completion of the reaction by measuring the NCO value, component (A-5) with a weight average molecular weight of 39,000 and an average number of acryloyl groups of 3 was obtained. .

Comparative manufacturing example 1
827 parts of PPG2000, 115 parts of IPDI, 0.4 parts of MQ, and 0.1 part of stannous octylate were added to a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, and the temperature was raised to 70°C and kept for 3 hours. After that, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 7 parts of HEA and a mixture of pentaerythritol triacrylate/pentaerythritol tetraacrylate (trade name: "Aronix M-306", manufactured by Toagosei Co., Ltd., weight ratio of pentaerythritol triacrylate 65 to 70%) 51 Component (E-1) with a weight average molecular weight of 17,000 and an average number of acryloyl groups of 4.8 was obtained by adding 50% of the weight average molecular weight of 17,000 and keeping the temperature at 70°C for 2 hours, and confirming the completion of the reaction by measuring the NCO value. Obtained.

Comparative manufacturing example 2
747 parts of PPG2000, 166 parts of IPDI, 0.4 parts of MQ, and 0.1 part of stannous octylate were added to a reaction apparatus equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, and the temperature was raised to 70°C and kept for 3 hours. After that, an isocyanate group-terminated urethane prepolymer as an intermediate was obtained. Subsequently, 87 parts of HEA was added, kept at 70°C for 2 hours, and the completion of the reaction was confirmed by measuring the NCO value. Got the ingredients.

Example 1
(A-1) component, isobornyl acrylate (hereinafter referred to as IBOA) as the (B) component, 4-hydroxybutyl acrylate (hereinafter referred to as 4-HBA) as the (C) component, and 1-hydroxycyclohexyl as the photopolymerization initiator. Phenyl ketone (trade name: "Omnirad184", manufactured by IGM Resins) and diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (trade name: "JR CURE TPO", manufactured by Arc Co., Ltd.) are shown in Table 1. They were mixed at the same content ratio to obtain an active energy ray-curable adhesive composition.

Examples 2 to 9, Comparative Examples 1 to 7
The compositions and content ratios shown in Table 1 were mixed to obtain active energy ray-curable pressure-sensitive adhesive compositions.

(Preparation of hard coat agent)
500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: "NK Ester A-9550", manufactured by Shin Nakamura Chemical Co., Ltd.), 1-hydroxycyclohexylphenyl ketone (trade name) as a photopolymerization initiator A hard coat agent was prepared by mixing 10 parts of "Omnirad 184" (manufactured by IGM Resins) and 500 parts of methyl ethyl ketone as a diluting solvent.

The following items were evaluated for the active energy ray-curable adhesive compositions of each Example and Comparative Example. The results are shown in Table 1.

The hard coating agent was applied to the adhesion treated surface of a 100 μm thick polyester film (trade name: "Cosmoshine A4100", manufactured by Toyobo Co., Ltd., hereinafter referred to as A4100) using a bar coater to a film thickness of 10 μm. After drying at 80° C. for 1 minute, 100 mJ/cm ² of ultraviolet light was irradiated using a 120 W/cm high-pressure mercury lamp (manufactured by Iwasaki Electric Co., Ltd.). Next, the pressure-sensitive adhesive composition of Example 1 was applied to the back side of the obtained PET film with a hard coat layer using a commer coater to a film thickness of 50 μm, and then a 50 μm thick light-release treated polyester After laminating a film (product name: "SP-PET-01-38BU", manufactured by Panac Co., Ltd.) (hereinafter referred to as "released PET"), using a 120 W/cm high-pressure mercury lamp (manufactured by Iwasaki Electric Co., Ltd.) Then, ultraviolet rays were irradiated from the peeled PET side at a cumulative light intensity of 900 mJ/cm ² to produce a laminate (1) (see FIG. 1). Next, after peeling off the release PET from the laminate (1), the adhesive layer side was bonded to a glass plate using a 2 kg roller to produce a laminate (2) (A4100/adhesive layer/glass plate) (Fig. 2), and was left for 24 hours at a temperature of 25° C. and a humidity of 50%. Laminates were similarly produced for the pressure-sensitive adhesive compositions of Examples 2 to 9 and Comparative Examples 1 to 7, respectively. The layer structures of the resulting laminates (1) and (2) are shown in FIGS. 3 and 4, respectively.

<Adhesive strength>
Cut out each laminate (2) to a width of 25 mm, and use a single column material testing machine (product name: "STA-1225", manufactured by A&D Co., Ltd.) to test the laminate at a 180° angle from the glass plate. The adhesive force (unit: mN/25 mm) was measured by peeling in the direction at a speed of 300 mm/min. The larger the value, the higher the adhesive strength.

<Pencil hardness>
In accordance with JIS K5600-5-4, a load of 500 g was applied to the surface of the hard coat layer of the laminate (2) using a pencil having a hardness of HB, and the presence or absence of scratches was visually confirmed. This operation was performed 5 times, and the number of scratches was taken as the measured value. A case where the number of scratches was 2 or less was considered good. A pencil with hardness F was also measured in the same manner.

<Durability>
After each laminate was allowed to stand in a constant temperature and humidity bath for 500 hours at a temperature of 85° C. and a humidity of 85%, the durability of the cured product was evaluated based on the following criteria.
<Evaluation criteria>
○: No peeling of the base material, misalignment of the cured product, bubbles in the cured product, or whitening of the cured product ×: Peeling of the base material, misalignment of the cured product, bubbles in the cured product, or whitening of the cured product at least one defect occurs

<Storage modulus>
Each adhesive composition was applied onto a 75 μm thick heavy release treated polyester film (manufactured by Panac Co., Ltd., trade name: “SP-PET-03-75BU”) so that the film thickness after curing was 200 μm. Then, the release-treated side of a 38 μm thick lightly release-treated polyester film (manufactured by Panac Co., Ltd., trade name: "SP-PET-01-38BU") was attached to the coating layer. Next, ultraviolet rays were irradiated in the atmosphere using a 120 W/cm high-pressure mercury lamp (manufactured by Iwasaki Electric Co., Ltd.) at an irradiation intensity of 100 mW/cm ² and an integrated light amount of 900 mJ/cm ² to coat the adhesive layer. A laminate (light release treated polyester film/adhesive layer/heavy release treated polyester film) was prepared. Next, a 1 cm x 1 cm test piece was cut from the laminate, and then the light release treated polyester film and the heavy release treated polyester film were peeled off. Five adhesive layers were prepared in a similar manner and then laminated to form an adhesive layer with a thickness of about 1 mm. The dynamic viscoelasticity of the adhesive layer (approximately 1 mm thick) was measured using a commercially available rheometer (product name: "MCR302", manufactured by Anton Paar) under the following conditions, and from the obtained value it was determined that storage at a temperature of 25 ° C. The elastic modulus G' (unit: MPa) was determined.

Deformation mode: Torsion Measurement frequency: 1Hz
Distortion: 0.01~1% AUTO setting Temperature increase rate: 3℃/min Measurement temperature: -50~100℃
Shape: Parallel plate 8.0mmφ

As used herein, storage modulus (G') is a value that is proportional to the maximum energy stored over a loading cycle and represents the stiffness of the adhesive layer. Note that rigidity refers to the difficulty of deformation due to external forces such as bending and torsion. The larger the value of the storage modulus at a temperature of 25° C. and 1 Hz, the higher the rigidity of the adhesive layer. The adhesive layer of the present invention has a storage modulus G' of 0.5 MPa or more at 25° C. and 1 Hz, so that the laminate including the adhesive layer of the present invention can prevent a decrease in the hardness of the hard coat layer. preferable.

*1: Expressed by weight based on the total of 100 parts by weight of component (A), component (B), component (C), and other monomers.

The component symbols and abbreviations in Table 1 mean the following compounds.
<(A) component>
・(A-1) to (A-5): Polyurethane (meth)acrylates of Production Examples 1 to 5 (same order of composites)
・(E-1) to (E-2): Polyurethane (meth)acrylate of Comparative Production Examples 1 and 2 (composite same order)
<(B) component>
・IBOA: Isobornyl acrylate, product name: "Light acrylate IB-XA", manufactured by Kyoeisha Chemical Co., Ltd. (Tg = 94°C)
・TMCHA: 3,3,5-trimethylcyclohexyl acrylate, trade name: "Viscoat #196", manufactured by Osaka Organic Chemical Industry Co., Ltd. (Tg: 52°C)
<Other monomers>
・2EHA: 2-ethylhexyl acrylate, manufactured by Mitsubishi Chemical Corporation (Tg: -70°C)
・CHA: Cyclohexyl acrylate (Tg: 15°C), product name: "Viscoat #155", manufactured by Osaka Organic Chemical Industry Co., Ltd. <(C) component>
・4-HBA: 4-hydroxybutyl acrylate ・HEA: 2-hydroxyethyl acrylate <(D) component>
KE-100: Disproportionated rosin ester (manufactured by Arakawa Chemical Co., Ltd., trade name: "Pine Crystal KE-100")
<Photopolymerization initiator>
・Omni184: 1-hydroxycyclohexylphenyl ketone (trade name: "Omnirad184", manufactured by IGM Resins)
・TPO: diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (product name: "JR CURE TPO", manufactured by Arc Co., Ltd.)

1 Adhesive sheet (hard coat layer/base material/adhesive layer/release sheet)
2 Laminate (hard coat layer/base material/adhesive layer/glass)
3a Hard coat agent 3b Hard coat layer 4 Base material (100 μm PET film)
5a Adhesive composition 5b Adhesive layer 6 Release-treated PET film 7 Adherent (glass)

Claims (8)

It is a reaction product of polyol (a1), polyisocyanate (a2), and mono(meth)acrylate (a3-1) having a hydroxy group or mono(meth)acrylate (a3-2) having an isocyanate group, and has one molecule. A polyurethane (meth)acrylate (A) having an average number of (meth)acryloyl groups of 1 to 4 and a weight average molecular weight of 26,000 to 90,000;
Monomer (B) having one ethylenically unsaturated double bond in the molecule and having no hydroxyl group and having a glass transition temperature of 40°C or higher when made into a homopolymer (nitrogen atom and unsaturated bond ) ) , and
Monomer (C) having one ethylenically unsaturated double bond and a hydroxy group in the molecule
and the content ratio of component (B) is 35 to 75% by mass in the total of 100% by mass of component (A), component (B) and component (C),
An active energy ray-curable adhesive composition (excluding those containing styrene resin) in which the component (a1) is a polyether polyol . The active energy ray-curable adhesive composition according to claim 1 , wherein component (B) contains an alicyclic mono(meth)acrylate. The active energy ray-curable adhesive composition according to claim 1 or 2 , wherein component (C) contains monohydroxyalkyl mono(meth)acrylate. The active energy ray-curable adhesive composition according to any one of claims 1 to 3 , further comprising (D) a tackifying resin. An adhesive layer of the active energy ray-curable adhesive composition according to any one of claims 1 to 4 . The adhesive layer according to claim 5 , having a storage modulus G' of 0.5 MPa or more at a temperature of 25° C. and a frequency of 1 Hz. A laminate having an adhesive layer according to claim 5 or 6 on at least one side of a base material. A laminate having the adhesive layer according to claim 5 or 6 on one side of a base material and a hard coat layer on the other side.